WO2013066841A1 - Inorganic nanoporous membranes for high temperature pretreatment of lignocellulosic biomass - Google Patents
Inorganic nanoporous membranes for high temperature pretreatment of lignocellulosic biomass Download PDFInfo
- Publication number
- WO2013066841A1 WO2013066841A1 PCT/US2012/062519 US2012062519W WO2013066841A1 WO 2013066841 A1 WO2013066841 A1 WO 2013066841A1 US 2012062519 W US2012062519 W US 2012062519W WO 2013066841 A1 WO2013066841 A1 WO 2013066841A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane element
- approximately
- layer
- inorganic
- separating
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 74
- 239000002029 lignocellulosic biomass Substances 0.000 title description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000012546 transfer Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 26
- 150000001720 carbohydrates Chemical class 0.000 claims description 20
- 235000014633 carbohydrates Nutrition 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002028 Biomass Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002551 biofuel Substances 0.000 abstract description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 22
- 239000012466 permeate Substances 0.000 description 20
- 230000014759 maintenance of location Effects 0.000 description 18
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 14
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 14
- 239000012465 retentate Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008103 glucose Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 241000609240 Ambelania acida Species 0.000 description 11
- 239000010905 bagasse Substances 0.000 description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 10
- 235000000346 sugar Nutrition 0.000 description 9
- 241000219000 Populus Species 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001223 reverse osmosis Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000010907 stover Substances 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920001503 Glucan Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 alumina Chemical class 0.000 description 3
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229930014251 monolignol Natural products 0.000 description 3
- 125000002293 monolignol group Chemical group 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241001520808 Panicum virgatum Species 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Polymers 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 150000002972 pentoses Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- 108010059892 Cellulase Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000193448 Ruminiclostridium thermocellum Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229940119526 coniferyl alcohol Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 235000009048 phenolic acids Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- NFRXJXZFBLDZNB-UHFFFAOYSA-N syringylglycerol Chemical compound COC1=CC(C(=O)OCCO)=CC(OC)=C1O NFRXJXZFBLDZNB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
Definitions
- the present invention relates to nanoporous membranes for the pretreatment of lignocellulosic feedstocks and other applications.
- Lignocellulosic feedstocks have been proposed as an alternative fuel source for the production of bio-ethanol and other chemicals.
- exemplary feedstocks include corn stover, bagasse, switchgrass, pine and poplar.
- these feedstocks typically require pretreatment to overcome their inherent recalcitrance to attack by microorganisms and their enzymes.
- Existing methods of pretreatment include flow-through pretreatment and steam pretreatment.
- Flow-through pretreatment includes directing water through a bed of lignocellulosic feedstock. This method optionally includes the addition of mineral acids to promote hydrolysis of the feedstocks into fermentable sugars.
- Steam pretreatment by comparison, demonstrates lower material costs over flow-through methods while enhancing the reactivity of the resulting solids.
- known pretreatment methods involve the partial thermochemical depolymerization and degradation of carbohydrates and lignins in the feedstock.
- known flow-through and steam pretreatment methods include sugar losses and yield compounds inhibitory to fermentation. Accordingly, there remains a continued need for an improved pretreatment method to leverage the benefits of lignocellulosic feedstock as a potential fuel source.
- a system that can retain carbohydrates and lignins at pretreatment conditions while producing a superior concentrate of reactive organics.
- the inorganic membrane element for the pretreatment of lignocellulosic biomass provided.
- the inorganic membrane element includes a tubular structure having an inner separating layer, an outer supporting layer, and at least one intermediate layer interposed between the separating and supporting layers, where the separating layer is nanoporous to selectively retain solutes while permitting the transfer of high-temperature solvents therethrough.
- the inorganic membrane element is suitable for use in a pretreatment process to provide solubilized organics in concentrated form for the subsequent conversion into bio-fuels and other chemicals.
- the supportive, intermediate, and separative layers are formed of porous metal oxides such as alumina, carbon zirconia, silica and titania.
- the intermediate layer can additionally be formed of silicon carbide, and the supporting layer can additionally be formed of silicon carbide or porous metal.
- the layers can form a tubular single- or multi-channel composite structure in which a sieving separation mechanism allows solvents to permeate radially through the inorganic membrane.
- the nanoporous separating layer optionally includes a mean pore size of between approximately 0.5 nm and 10 nm.
- the supporting layer can define a pore size that differs from the separating layer pore size by an order of magnitude or more.
- the supporting layer pore size is approximately 2 to 10 microns in one embodiment.
- the intermediate layer includes an intermediate pore size to ensure the separative layer does not fill the larger pores of the supporting layer and thereby degrade membrane permeability.
- the intermediate layer defines a mean pore size of approximately 0.1 to 1.0 microns.
- the pretreatment process generally includes flowing water through a pretreatment reactor containing a bed of particulate lignocellulosic biomass, separating solubilized compounds from a hydrolyzate emerging from the reactor using the inorganic nanoporous membrane element, the stepwise removal of fractions enriched in solubilized organic components (e.g. arising from hemicellulose and lignin) and the recycling of a water- rich stream to the reactor.
- the pressurized hydrolyzate flow can contain solubilized organics having a molecular weight as low as a few hundred Daltons.
- the solubilized organics can include pentose, lignin, oligo and polysaccharides that can substantially increase the yield of lignocellulosic biomass in the production of bio-fuels.
- Fig. 1 is a diagram of an inorganic nanoporous membrane element in accordance with the present invention.
- FIG. 2 are perspective and elevational views of single- and multi-channel inorganic nanoporous membrane elements in accordance with the present invention.
- Fig. 3 is a first flow diagram of the pretreatment process of the present invention utilizing the inorganic membrane element of Fig. 1.
- FIG. 4 is a second flow diagram of the pretreatment process of the present invention utilizing the inorganic membrane element of Fig. 1
- Fig. 5 is a graph of illustrating the stepwise fractionation of carbohydrate fractions at different temperatures during membrane pretreatment.
- Fig. 6 is a graph illustrating corn stover carbohydrate concentrations.
- Fig. 7 are graphs illustrating corn stover carbohydrate concentrations including oligomers and monomers.
- Fig. 8 is a table illustrating carbohydrate retention for poplar feedstock.
- Fig. 9 is a table illustrating carbohydrate retention for bagasse feedstock.
- Fig. 10 is a GC-MS chart illustrating the separation and preferential permeation or removal of inhibitors.
- the invention as contemplated and disclosed herein includes an inorganic nanoporous membrane element and a method for the pretreatment of lignocellulosic biomass utilizing the nanoporous membrane element to separate low molecular weight solubilized organics at high temperatures and pressures (to maintain the solubilized fractions are in liquid form) for conversion into bio-fuels and for other applications.
- a nanoporous membrane element in accordance with an embodiment of the invention is illustrated in Fig. 1 and generally designated 10.
- the nanoporous membrane element 10 of the present embodiment includes a single- or multi-channel structure having an inner separating layer 12, an outer supporting layer 16, and at least one intermediate layer 14 interposed between the separating and supporting layers, where the separating layer 12 is nanoporous to selectively retain low organic weight solutes while permitting the transfer of high temperature solvents through the membrane.
- the inner nanoporous separating layer 12 includes a mean pore size selected to retain solutes having a molecular weight as low as a few hundred Daltons.
- the mean pore size is between 0.5 nm and 2 nm, while in other embodiments the mean pore size can vary outside of this range, including for example 2 nm, 4 nm, 5 nm or 10 nm.
- the separating layer 12 includes a thickness of less than 1 micron up to approximately 10 microns, and can be formed from a suitable ceramic, including metal oxides such as alumina, titania, silica and zirconia, as well as carbon.
- the intermediate layer 14 includes an intermediate pore size to ensure the separative layer 12 does not fill the larger pores of the supporting layer 16 and thereby degrade membrane permeability.
- the intermediate layer 14 defines a mean pore size of approximately 0.1 to 1.0 microns, which is less than the mean pore size of the supporting layer 16, but greater than the mean pore size of the separating layer 12.
- the membrane 10 can include two or more intermediate layers each having a stepped increase in pore size over the adjacent inner intermediate layer.
- the intermediate layer can have a thickness of between 10 microns to 100 microns, again depending on the material utilized. Suitable materials include, but are not limited to, ceramics such as alumina, titania, silica and zirconia, as well as silicon carbide and carbon for example.
- the outer supporting layer 16 provides mechanical strength to withstand an outward pressure differential applied across the membrane element 10.
- the supporting layer 16 can have a thickness generally between 0.5 mm and 5 mm.
- the supporting layer 16 can be formed of any suitably strong porous material, including porous metal such as stainless steel and nickel, carbon, silicon carbide or a metal oxide such as alumina, titania, silica and zirconia.
- the mean pore size for the supporting layer typically differs from the separating layer pore size by an order of magnitude or more.
- the supporting layer pore size can be approximately 2 to 10 microns in the illustrated embodiment, or roughly three to four orders of magnitude greater than the nanoporous pore size of the separating layer 12.
- This type of composite micro structure has the potential to offer the optimal membrane permeability, which can be an important factor to maximize overall throughput and process yield.
- Each layer can be formed according to conventional methods and subsequently thermally bonded to its adjoining layer to form a tubular single- or multichannel composite structure.
- the outer diameter can be approximately 10 to 12 mm
- the channel diameter can be approximately 7 to 10 mm.
- each channel can have a diameter of between 1 and 6 mm.
- a solution is directed through the one or more channels in the nanoporous membrane element 10.
- the transmembrane pressure i.e. the pressure differential applied across the membrane 10 element
- the solvent permeates through the nanoporous layer 12 while solutes are prevented from permeating through the nanoporous layer.
- the mechanism of transport across the membrane element 10 is a sieving action, which differs from reverse osmosis, in which the solute must first solubilize in a dense separating layer and then diffuse across the membrane.
- the nanoporous membrane 10 is superior to reserve osmosis membranes in many applications because it is not limited by diffusability and solubility considerations.
- Typical pressure differentials for the nanoporous membrane element 10 include 200 psig to 550 psig. These values depend on feed characteristics and make separations possible in the liquid phase, preventing vaporization of volatile constituents in the pretreatment process. This pressure differential is significantly less than the pressure differential applied in reverse osmosis membranes, for example, which can require pressure differentials of greater than 1000 psig to overcome low diffusivity and solubility through a dense separating layer and to provide for reasonable flux for industrial scale processing. In addition, the nanoporous membrane element 10 is less prone to fouling when compared to reverse osmosis membranes.
- the sugars or lignins that clog the pores in the nanoporous separating layer 12 can be dissolved with the application of dilute solution ( ⁇ 1 wt. %) of sodium hydroxide for example.
- dilute solution ⁇ 1 wt. % of sodium hydroxide for example.
- the caustic or acid chemical depending on the solutes cannot easily permeate through the fouled dense separating layer and thereby may not regenerate efficiently for long term use due to the substantially lowered permeability of the reverse osmosis membrane due to fouling under process conditions.
- a Flow-Through Recycle (FTR) process for the pretreatment of lignocellulosic biomass in which the inorganic nanoporous membrane element 10 is utilized to separate low molecular weight organics at high temperatures.
- the FTR process generally includes flowing water through a pretreatment reactor containing a bed of particulate lignocellulosic biomass, separating solubilized compounds from the reactor using the inorganic nanoporous membrane element, removing retentate fractions enriched in solubilized organic components, and recycling water to the pretreatment reactor.
- a biomass substrate is first suspended in a flow-through reactor.
- the biomass can include, but is not limited to, corn stover, bagasse, switchgrass, poplar, pine and combinations thereof.
- the reactor chamber is then heated to between 180°C and 230°C for a predetermined period, for example between 12 to 20 minutes, followed by the introduction of pressurized water heated to between 170°C and 210°C to create a hydrolyzate exit stream.
- the reactor chamber can be heated to other temperatures as desired, and the water temperature can be varied as well.
- the pretreatment process can optionally include one or more dilute acid treatments to promote hydrolysis of the feedstocks into fermentable compounds. In the present embodiment, however, no acid treatments are utilized.
- the hydrolyzate exit stream contains solubilized organics including diluted amounts of reactive solids from the pretreatment reactor.
- the reactive solids can include glucose, xylose, pentose, lignin, oligo and polysaccharides from the lignocellulosic biomass.
- the hydrolyzate exit stream is then pressurized to between 200 psi and 550 psi before membrane separation, during which time its mean temperature can remain up to 230°C depending on the maximum operating pressure to perform the desired separation and fractionation in the liquid phase.
- the pressurized hydrolyzate stream is then directed through the one or more channels in a nanoporous inorganic membrane element to generate a retentate having an increased concentration of reactive solids.
- the hydrolyzate exit stream is at or near the pretreatment reaction temperature and pressure.
- the size of the solutes excluded in this separation are on the order of one nanometer.
- the driving force of the separation process is the pressure difference between the retentate and the permeate side at the separation layer 12 of the membrane 10. The permeate is then recycled to the flow- through reactor as shown in Fig. 3, and the retentate (enriched in sugars) is thereafter fractionated and fermented to produce ethanol, for example.
- the FTR pretreatment process can also include a recirculation of the retentate.
- the water supply is first pressurized and heated within a reservoir 20 to between 100°C and 200°C. Pressurized water from the reservoir 20 is directed through the suspended lignocellulosic biomass and then through a high temperature pump 22 and a preheater 24. The resulting high temperature, high pressure biomass hydrolyzate is directed through a channel defined in the inorganic membrane element 10. The permeate is collected at a collection reservoir 26 while the retentate is recirculated to the heated reservoir 20. In this configuration, no chemicals (other then water) are added to prepare the hydrolyzate of the biomass suspension.
- this configuration does not include the addition of an acid or a base to the biomass suspension, which might otherwise convert certain organic solutes into products that are inhibitory to fermentation.
- the configuration as shown in Fig. 4 can also be utilized to clean the membrane element 10 of fouling, in which a caustic solution is utilized in place of the biomass hydrolyzate. If caustic solutions are not utilized, foulants can also be removed with the application of high temperature steam to membrane element 10.
- inorganic nanoporous membranes are advantageous over widely used polymeric membranes, which are temperature limited to substantially less than 100°C.
- the use of inorganic nanoporous membranes is also advantageous over reverse osmosis membranes, which are typically operated at higher pressures (>1000 psig) to overcome the physical resistance of a dense membrane (due to the low diffusivity and solubility of the solutes), and which are more prone to fouling.
- the inorganic nanoporous membrane element 10 provides increased flux, separation and ease of regeneration, while also selectively retaining sugars, lignin and proteins and recycling water back to the pretreatment reactor.
- the FTR pretreatment method of the present invention can achieve highly reactive solids, minimal formation of sugar degradation products, a non-inhibitory hydrolyzate, reasonable energy requirements, and fractionation and recovery of solubilized biomass components in concentrated form.
- Laboratory testing confirmed the effectiveness of the nanoporous membrane element 10 in retaining select carbohydrates in the hydrolyzate feed.
- the feed side pressure was maintained at 300 psi to 450 psi while the permeate side pressure was maintained at 100 psi to 350 psi.
- the feed flow rate was 15 ml/min, and the permeate flow rate was initially 3 ml/min, transitioning to 1 ml/min over a 30-40 min run.
- the contact time of the biomass hydrolyzate with the membrane was limited to less than 10 minutes to minimize the potential for sugar degradation at high temperatures.
- the carbohydrate retention rate for poplar at the start of the test run was determined to be 98.5%
- Fig. 6 depicts the total glucose and xylose concentration in the retentate and permeate during the 26 minute test run.
- the percent of glucose/xylose in the permeate was 1.52% for glucose and 0.31% for xylose.
- the permeate xylose was predominantly oligomer as shown in Fig. 7, and the permeate glucose was approximately fifty percent monomer as also shown in Fig. 7.
- Figs. 8-9 are graphs illustrating the retention of select carbohydrates in laboratory testing of a membrane having a nanoporous titania separating layer with a mean pore size of 2.5 nm.
- poplar hydrolyzate feed was heated to between 185°C and 215°C and pressurized to between 300 psig and 500 psig.
- the glucose retention was above 98%
- the xylose retention was above 97%
- the arabinose retention was at or above 99%.
- bagasse hydrolyzate feed was heated to between 190°C and
- the hydrolyzate feed can contain low molecular weight organics that potentially inhibit the downstream fermentation of a fractionated retentate.
- These inhibitors can include monolignols formed in the breakdown of lignin and can also include phenolic acids/aldehydes.
- Fig. 10 is a Gas Chromatography-Mass Spectrometry (GC-MS) chart illustrating the removal of inhibitors from a bagasse hydrolyzate feed. As shown in Fig. 10, coniferyl alcohol (a monolignol) demonstrated a lowered concentration in the retentate relative to the feed and demonstrated a corresponding increase in concentration in the permeate.
- GC-MS Gas Chromatography-Mass Spectrometry
- Sinapyl alcohol (a monolignol) and syringylglycerol (an aldehyde) also demonstrated a relative decrease in concentration in the retentate relative to the feed and demonstrated a corresponding increase in concentration in the permeate.
- the remaining peaks in Fig. 10 illustrate the desired retention of low molecular weight sugars in the bagasse retentate.
- the inorganic membrane 10 demonstrated the transfer of known inhibitors to the permeate while retaining desired low molecular weight organics for subsequent fractionation and fermentation into bio-fuels or other chemicals.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
An inorganic membrane element and a pretreatment process are provided. The inorganic membrane element includes a tubular structure having an inner separating layer, an outer supporting layer, and at least one intermediate layer interposed between the separating and supporting layers, where the separating layer is nanoporous to selectively retain solutes while permitting the transfer of high-temperature solvents therethrough. The pretreatment process utilizes the inorganic membrane element to provide solubilized organics in concentrated form for the subsequent conversion into bio-fuels and other chemicals.
Description
INORGANIC NANOPOROUS MEMBRANES FOR HIGH TEMPERATURE
PRETREATMENT OF LIGNOCELLULOSIC BIOMASS
[0001] This invention was made with government support under Contract No. DE-
AC05-00OR22725 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to nanoporous membranes for the pretreatment of lignocellulosic feedstocks and other applications.
[0003] Lignocellulosic feedstocks have been proposed as an alternative fuel source for the production of bio-ethanol and other chemicals. Exemplary feedstocks include corn stover, bagasse, switchgrass, pine and poplar. However, these feedstocks typically require pretreatment to overcome their inherent recalcitrance to attack by microorganisms and their enzymes. Existing methods of pretreatment include flow-through pretreatment and steam pretreatment. Flow-through pretreatment includes directing water through a bed of lignocellulosic feedstock. This method optionally includes the addition of mineral acids to promote hydrolysis of the feedstocks into fermentable sugars. Steam pretreatment, by comparison, demonstrates lower material costs over flow-through methods while enhancing the reactivity of the resulting solids.
[0004] Despite their advantages, known pretreatment methods involve the partial thermochemical depolymerization and degradation of carbohydrates and lignins in the feedstock. In particular, known flow-through and steam pretreatment methods include sugar losses and yield compounds inhibitory to fermentation. Accordingly, there remains a continued need for an improved pretreatment method to leverage the benefits of lignocellulosic feedstock as a potential fuel source. In addition, there remains a continued need for a system that can retain carbohydrates and lignins at pretreatment conditions while producing a superior concentrate of reactive organics.
SUMMARY OF THE INVENTION
[0005] An inorganic membrane element for the pretreatment of lignocellulosic biomass provided. The inorganic membrane element includes a tubular structure having an inner separating layer, an outer supporting layer, and at least one intermediate layer interposed between the separating and supporting layers, where the separating layer is nanoporous to selectively retain solutes while permitting the transfer of high-temperature solvents therethrough. The inorganic membrane element is suitable for use in a pretreatment process to provide solubilized organics in concentrated form for the subsequent conversion into bio-fuels and other chemicals.
[0006] In one embodiment, the supportive, intermediate, and separative layers are formed of porous metal oxides such as alumina, carbon zirconia, silica and titania. The intermediate layer can additionally be formed of silicon carbide, and the supporting layer can additionally be formed of silicon carbide or porous metal. The layers can form a tubular single- or multi-channel composite structure in which a sieving separation mechanism allows solvents to permeate radially through the inorganic membrane.
[0007] The nanoporous separating layer optionally includes a mean pore size of between approximately 0.5 nm and 10 nm. The supporting layer can define a pore size that differs from the separating layer pore size by an order of magnitude or more. For example, the supporting layer pore size is approximately 2 to 10 microns in one embodiment. The intermediate layer includes an intermediate pore size to ensure the separative layer does not fill the larger pores of the supporting layer and thereby degrade membrane permeability. In one embodiment, the intermediate layer defines a mean pore size of approximately 0.1 to 1.0 microns.
[0008] The pretreatment process generally includes flowing water through a pretreatment reactor containing a bed of particulate lignocellulosic biomass, separating
solubilized compounds from a hydrolyzate emerging from the reactor using the inorganic nanoporous membrane element, the stepwise removal of fractions enriched in solubilized organic components (e.g. arising from hemicellulose and lignin) and the recycling of a water- rich stream to the reactor. The pressurized hydrolyzate flow can contain solubilized organics having a molecular weight as low as a few hundred Daltons. The solubilized organics can include pentose, lignin, oligo and polysaccharides that can substantially increase the yield of lignocellulosic biomass in the production of bio-fuels.
[0009] These and other features and advantages of the present invention will become apparent from the following description of the invention, when viewed in accordance with the accompanying drawings and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Fig. 1 is a diagram of an inorganic nanoporous membrane element in accordance with the present invention.
[0011] Fig. 2 are perspective and elevational views of single- and multi-channel inorganic nanoporous membrane elements in accordance with the present invention.
[0012] Fig. 3 is a first flow diagram of the pretreatment process of the present invention utilizing the inorganic membrane element of Fig. 1.
[0013] Fig. 4 is a second flow diagram of the pretreatment process of the present invention utilizing the inorganic membrane element of Fig. 1
[0014] Fig. 5 is a graph of illustrating the stepwise fractionation of carbohydrate fractions at different temperatures during membrane pretreatment.
[0015] Fig. 6 is a graph illustrating corn stover carbohydrate concentrations.
[0016] Fig. 7 are graphs illustrating corn stover carbohydrate concentrations including oligomers and monomers.
[0017] Fig. 8 is a table illustrating carbohydrate retention for poplar feedstock.
[0018] Fig. 9 is a table illustrating carbohydrate retention for bagasse feedstock.
[0019] Fig. 10 is a GC-MS chart illustrating the separation and preferential permeation or removal of inhibitors.
DETAILED DESCRIPTION OF THE CURRENT EMBODIMENTS
[0020] The invention as contemplated and disclosed herein includes an inorganic nanoporous membrane element and a method for the pretreatment of lignocellulosic biomass utilizing the nanoporous membrane element to separate low molecular weight solubilized organics at high temperatures and pressures (to maintain the solubilized fractions are in liquid form) for conversion into bio-fuels and for other applications.
I. Nanoporous Membrane
[0021] A nanoporous membrane element in accordance with an embodiment of the invention is illustrated in Fig. 1 and generally designated 10. The nanoporous membrane element 10 of the present embodiment includes a single- or multi-channel structure having an inner separating layer 12, an outer supporting layer 16, and at least one intermediate layer 14 interposed between the separating and supporting layers, where the separating layer 12 is nanoporous to selectively retain low organic weight solutes while permitting the transfer of high temperature solvents through the membrane.
[0022] The inner nanoporous separating layer 12 includes a mean pore size selected to retain solutes having a molecular weight as low as a few hundred Daltons. In the present embodiment, the mean pore size is between 0.5 nm and 2 nm, while in other embodiments the mean pore size can vary outside of this range, including for example 2 nm, 4 nm, 5 nm or 10 nm. The separating layer 12 includes a thickness of less than 1 micron up to approximately 10 microns, and can be formed from a suitable ceramic, including metal oxides such as alumina, titania, silica and zirconia, as well as carbon.
[0023] The intermediate layer 14 includes an intermediate pore size to ensure the separative layer 12 does not fill the larger pores of the supporting layer 16 and thereby degrade membrane permeability. In one embodiment, the intermediate layer 14 defines a
mean pore size of approximately 0.1 to 1.0 microns, which is less than the mean pore size of the supporting layer 16, but greater than the mean pore size of the separating layer 12. While only one intermediate layer 14 is shown in Fig. 1, the membrane 10 can include two or more intermediate layers each having a stepped increase in pore size over the adjacent inner intermediate layer. Where a single intermediate layer 14 is used as shown in Fig. 1, the intermediate layer can have a thickness of between 10 microns to 100 microns, again depending on the material utilized. Suitable materials include, but are not limited to, ceramics such as alumina, titania, silica and zirconia, as well as silicon carbide and carbon for example.
[0024] The outer supporting layer 16 provides mechanical strength to withstand an outward pressure differential applied across the membrane element 10. Depending on the pressure differential and the supporting layer material, the supporting layer 16 can have a thickness generally between 0.5 mm and 5 mm. The supporting layer 16 can be formed of any suitably strong porous material, including porous metal such as stainless steel and nickel, carbon, silicon carbide or a metal oxide such as alumina, titania, silica and zirconia. The mean pore size for the supporting layer typically differs from the separating layer pore size by an order of magnitude or more. For example, the supporting layer pore size can be approximately 2 to 10 microns in the illustrated embodiment, or roughly three to four orders of magnitude greater than the nanoporous pore size of the separating layer 12. This type of composite micro structure has the potential to offer the optimal membrane permeability, which can be an important factor to maximize overall throughput and process yield.
[0025] Each layer can be formed according to conventional methods and subsequently thermally bonded to its adjoining layer to form a tubular single- or multichannel composite structure. In a single-channel membrane as shown in Fig. 1, the outer diameter can be approximately 10 to 12 mm, and the channel diameter can be approximately 7 to 10 mm. In a multi-channel configuration as shown in Fig. 2, each channel can have a
diameter of between 1 and 6 mm. These dimensions can vary from application to application however, and can include diameters outside the above ranges if desired for the particular application. In addition, other geometries are possible, including planar multi-layer membranes for example.
[0026] During use, a solution is directed through the one or more channels in the nanoporous membrane element 10. If the transmembrane pressure, i.e. the pressure differential applied across the membrane 10 element, is sufficient to overcome the minimum pressure required to keep all feed components in the liquid phase (i.e. prevents volatilization of water and some of the solubilized feed constituents), the solvent permeates through the nanoporous layer 12 while solutes are prevented from permeating through the nanoporous layer. The mechanism of transport across the membrane element 10 is a sieving action, which differs from reverse osmosis, in which the solute must first solubilize in a dense separating layer and then diffuse across the membrane. Thus, the nanoporous membrane 10 is superior to reserve osmosis membranes in many applications because it is not limited by diffusability and solubility considerations.
[0027] Typical pressure differentials for the nanoporous membrane element 10 include 200 psig to 550 psig. These values depend on feed characteristics and make separations possible in the liquid phase, preventing vaporization of volatile constituents in the pretreatment process. This pressure differential is significantly less than the pressure differential applied in reverse osmosis membranes, for example, which can require pressure differentials of greater than 1000 psig to overcome low diffusivity and solubility through a dense separating layer and to provide for reasonable flux for industrial scale processing. In addition, the nanoporous membrane element 10 is less prone to fouling when compared to reverse osmosis membranes. The sugars or lignins that clog the pores in the nanoporous separating layer 12 can be dissolved with the application of dilute solution (<1 wt. %) of sodium hydroxide for example. In reverse osmosis membranes, however, the caustic or acid
chemical (depending on the solutes) cannot easily permeate through the fouled dense separating layer and thereby may not regenerate efficiently for long term use due to the substantially lowered permeability of the reverse osmosis membrane due to fouling under process conditions.
II. Pretreatment Process
[0028] A Flow-Through Recycle (FTR) process for the pretreatment of lignocellulosic biomass is provided, in which the inorganic nanoporous membrane element 10 is utilized to separate low molecular weight organics at high temperatures. The FTR process generally includes flowing water through a pretreatment reactor containing a bed of particulate lignocellulosic biomass, separating solubilized compounds from the reactor using the inorganic nanoporous membrane element, removing retentate fractions enriched in solubilized organic components, and recycling water to the pretreatment reactor.
[0029] More specifically, and with reference to Fig. 3, a biomass substrate is first suspended in a flow-through reactor. The biomass can include, but is not limited to, corn stover, bagasse, switchgrass, poplar, pine and combinations thereof. The reactor chamber is then heated to between 180°C and 230°C for a predetermined period, for example between 12 to 20 minutes, followed by the introduction of pressurized water heated to between 170°C and 210°C to create a hydrolyzate exit stream. The reactor chamber can be heated to other temperatures as desired, and the water temperature can be varied as well. In some applications, the pretreatment process can optionally include one or more dilute acid treatments to promote hydrolysis of the feedstocks into fermentable compounds. In the present embodiment, however, no acid treatments are utilized.
[0030] The hydrolyzate exit stream contains solubilized organics including diluted amounts of reactive solids from the pretreatment reactor. For example, the reactive solids can include glucose, xylose, pentose, lignin, oligo and polysaccharides from the lignocellulosic biomass. The hydrolyzate exit stream is then pressurized to between 200 psi
and 550 psi before membrane separation, during which time its mean temperature can remain up to 230°C depending on the maximum operating pressure to perform the desired separation and fractionation in the liquid phase. The pressurized hydrolyzate stream is then directed through the one or more channels in a nanoporous inorganic membrane element to generate a retentate having an increased concentration of reactive solids. When high pressure sufficient to produce acceptable flux under liquid phase conditions is applied to the feed side of the membrane element, water is forced through the nanoporous structure of the membrane surface while the solutes are largely rejected. During this separation, the hydrolyzate exit stream is at or near the pretreatment reaction temperature and pressure. The size of the solutes excluded in this separation are on the order of one nanometer. The driving force of the separation process is the pressure difference between the retentate and the permeate side at the separation layer 12 of the membrane 10. The permeate is then recycled to the flow- through reactor as shown in Fig. 3, and the retentate (enriched in sugars) is thereafter fractionated and fermented to produce ethanol, for example.
[0031] The FTR pretreatment process can also include a recirculation of the retentate.
Referring now to Fig. 4, the water supply is first pressurized and heated within a reservoir 20 to between 100°C and 200°C. Pressurized water from the reservoir 20 is directed through the suspended lignocellulosic biomass and then through a high temperature pump 22 and a preheater 24. The resulting high temperature, high pressure biomass hydrolyzate is directed through a channel defined in the inorganic membrane element 10. The permeate is collected at a collection reservoir 26 while the retentate is recirculated to the heated reservoir 20. In this configuration, no chemicals (other then water) are added to prepare the hydrolyzate of the biomass suspension. For example, this configuration does not include the addition of an acid or a base to the biomass suspension, which might otherwise convert certain organic solutes into products that are inhibitory to fermentation. The configuration as shown in Fig. 4 can also be utilized to clean the membrane element 10 of fouling, in which a caustic
solution is utilized in place of the biomass hydrolyzate. If caustic solutions are not utilized, foulants can also be removed with the application of high temperature steam to membrane element 10.
[0032] To reiterate, separation of the retentate is performed at high temperatures which minimize the impact of carbohydrate and lignin degradation while providing a clean sugar stream. The use of inorganic nanoporous membranes is advantageous over widely used polymeric membranes, which are temperature limited to substantially less than 100°C. The use of inorganic nanoporous membranes is also advantageous over reverse osmosis membranes, which are typically operated at higher pressures (>1000 psig) to overcome the physical resistance of a dense membrane (due to the low diffusivity and solubility of the solutes), and which are more prone to fouling. In addition, the inorganic nanoporous membrane element 10 provides increased flux, separation and ease of regeneration, while also selectively retaining sugars, lignin and proteins and recycling water back to the pretreatment reactor.
[0033] The FTR pretreatment method of the present invention can achieve highly reactive solids, minimal formation of sugar degradation products, a non-inhibitory hydrolyzate, reasonable energy requirements, and fractionation and recovery of solubilized biomass components in concentrated form. Laboratory testing confirmed the effectiveness of the nanoporous membrane element 10 in retaining select carbohydrates in the hydrolyzate feed. Carbohydrate retention was evaluated for both poplar and bagasse according to the following formula: % retention = (g/L in feed - g/L in permeate) / (g/L in feed). During testing, the feed side pressure was maintained at 300 psi to 450 psi while the permeate side pressure was maintained at 100 psi to 350 psi. The feed flow rate was 15 ml/min, and the permeate flow rate was initially 3 ml/min, transitioning to 1 ml/min over a 30-40 min run. The contact time of the biomass hydrolyzate with the membrane was limited to less than 10 minutes to minimize the potential for sugar degradation at high temperatures. The
carbohydrate retention rate for poplar at the start of the test run was determined to be 98.5%
(glucose) and 97.4% (xylose), and the carbohydrate retention rate for bagasse was determined to be 99.4% (glucose) and 98.7% (xylose). At the end of the run the retention rates improved to 100% for poplar-glucose, poplar-xylose and bagasse-glucose and 99.2% for bagasse xylose. The water recovery was 15%-20%, and the permeate also showed partial removal (10-50%) of inhibitors such as 2-furfural which would help enhance reactivity and achieve a higher ethanol yield. With the use of a larger area module, combined with an increase in average permeate flux to greater than 50 liter/hr-m , water recovery can improve to between 50% and 80%. Additional laboratory testing confirmed the reactivity of select carbohydrates in the high-temperature retentate using a bagasse biomass. These results are shown in Fig. 5 with overall fractions of carbohydrates (arabinose, glucose and xylose) released at different temperatures.
[0034] Additional laboratory testing confirmed the membrane's excellent retention of corn stover carbohydrates in a hydrolyzate feed at 180°C to 190°C at 200 psig with a 30 ml/min flow rate. The separation resulted in a retentate flow rate of 26.9 ml/min and a permeate flow rate of 3.1 ml/min. For a single pass process, 10.3% of the volume of the hydrolyzate feed transfers across the membrane 10 to form the permeate. Fig. 6 depicts the total glucose and xylose concentration in the retentate and permeate during the 26 minute test run. The percent of glucose/xylose in the permeate was 1.52% for glucose and 0.31% for xylose. The permeate xylose was predominantly oligomer as shown in Fig. 7, and the permeate glucose was approximately fifty percent monomer as also shown in Fig. 7.
[0035] Figs. 8-9 are graphs illustrating the retention of select carbohydrates in laboratory testing of a membrane having a nanoporous titania separating layer with a mean pore size of 2.5 nm. In one evaluation, poplar hydrolyzate feed was heated to between 185°C and 215°C and pressurized to between 300 psig and 500 psig. The glucose retention was above 98%, the xylose retention was above 97% and the arabinose retention was at or above
99%. In another evaluation, bagasse hydrolyzate feed was heated to between 190°C and
205°C and pressurized to between 300 psig and 450 psig. The glucose retention was above 99%, the xylose retention was above 97% and the arabinose retention was at or above 96%, thereby increasing the carbohydrate retention by 15% to 20%. These results show nearly quantitative retention of carbohydrates with nanoporous inorganic membrane at pretreatment conditions. The reactivity of the concentrated carbohydrates were subsequently tested in C. thermocellum fermentation using a commercial cellulase, revealing a -80% glucan conversion on poplar and a -90% glucan conversion on bagasse. This represents a 15-20% increase over glucan conversion obtained using the conventional batch process.
[0036] As noted above, the hydrolyzate feed can contain low molecular weight organics that potentially inhibit the downstream fermentation of a fractionated retentate. These inhibitors can include monolignols formed in the breakdown of lignin and can also include phenolic acids/aldehydes. Fig. 10 is a Gas Chromatography-Mass Spectrometry (GC-MS) chart illustrating the removal of inhibitors from a bagasse hydrolyzate feed. As shown in Fig. 10, coniferyl alcohol (a monolignol) demonstrated a lowered concentration in the retentate relative to the feed and demonstrated a corresponding increase in concentration in the permeate. Sinapyl alcohol (a monolignol) and syringylglycerol (an aldehyde) also demonstrated a relative decrease in concentration in the retentate relative to the feed and demonstrated a corresponding increase in concentration in the permeate. The remaining peaks in Fig. 10 illustrate the desired retention of low molecular weight sugars in the bagasse retentate. Thus, the inorganic membrane 10 demonstrated the transfer of known inhibitors to the permeate while retaining desired low molecular weight organics for subsequent fractionation and fermentation into bio-fuels or other chemicals.
[0037] The above description is that of current embodiments of the invention.
Various alterations and changes can be made without departing from the spirit and broader aspects of the invention as defined in the appended claims, which are to be interpreted in
accordance with the principles of patent law including the doctrine of equivalents. Any reference to elements in the singular, for example, using the articles "a," "an," "the," or "said," is not to be construed as limiting the element to the singular.
Claims
1. A nanofiltration membrane element for biomass pretreatment, comprising: an inorganic separating layer;
an inorganic supporting layer spaced apart from the separating layer; and
an inorganic intermediate layer interposed between the supporting and separating layers, wherein the separating layer is nanoporous to selectively retain organic solutes while permitting the transfer of solvents therethrough.
2. The membrane element of claim 1 wherein the solutes are reactive carbohydrates and lignins and wherein the solvent includes pressurized hydrolyzate heated to between 170°C and 230°C.
3. The membrane element of claim 1 wherein the separating layer defines a thickness of between approximately 1 and 5 microns and a mean pore size of between approximately 0.5 and 10 nanometers.
4. The membrane element of claim 1 wherein the intermediate layer defines a thickness of between approximately 10 and 100 microns and a mean pore size of between approximately 0.1 to 1 microns.
5. The membrane element of claim 1 wherein the supporting layer defines a thickness of between approximately 0.5 and 5 mm and a mean pore size of between approximately 2 and 10 microns.
6. The membrane element of claim 1 wherein the separating layer is formed of a metal oxide selected from a group consisting of alumina, titania, silica, zirconia and carbon.
7. The membrane element of claim 1 wherein the intermediate layer is formed from one of a metal oxide, silicon carbide and carbon.
8. The membrane element of claim 1 wherein the supporting layer is formed from one of a metal oxide, silicon carbide, porous metal and carbon.
9. The membrane element of claim 1 further defining a single longitudinal channel having an inner diameter of between approximately 7 mm and 10 mm.
10. The membrane element of claim 1 further defining a plurality of longitudinal channels each having an inner diameter of between approximately 1 mm and 6 mm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/354,217 US20140263034A1 (en) | 2011-10-31 | 2012-10-30 | Inorganic nanoporous membranes for high temperature pretreatment of lignocellulosic biomass |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161553419P | 2011-10-31 | 2011-10-31 | |
US61/553,419 | 2011-10-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013066841A1 true WO2013066841A1 (en) | 2013-05-10 |
Family
ID=48192669
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2012/062519 WO2013066841A1 (en) | 2011-10-31 | 2012-10-30 | Inorganic nanoporous membranes for high temperature pretreatment of lignocellulosic biomass |
Country Status (2)
Country | Link |
---|---|
US (1) | US20140263034A1 (en) |
WO (1) | WO2013066841A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105268247A (en) * | 2014-07-23 | 2016-01-27 | 上海一鸣过滤技术有限公司 | Nanoscale porous metal filter medium and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7226657B1 (en) * | 1998-11-04 | 2007-06-05 | Baxter International Inc. | Element provided with a fibrin layer, preparation and use thereof |
US20100056369A1 (en) * | 2008-08-29 | 2010-03-04 | Yunfeng Gu | Methods of Making Inorganic Membranes |
US20110025306A1 (en) * | 2009-08-03 | 2011-02-03 | Microfier, Inc. | Method and Apparatus for the Purification and Analytical Evaluation of Highly Purified Liquids |
JP2011205987A (en) * | 2010-03-30 | 2011-10-20 | Toray Ind Inc | Method for producing xylose syrup |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8702759A (en) * | 1987-11-19 | 1989-06-16 | Hoogovens Groep Bv | METHOD FOR MANUFACTURING A MICRO-PERMEABLE MEMBRANE AND APPARATUS FOR APPLYING THIS MEMBRANE TO A CARRIER |
DE10107539A1 (en) * | 2001-02-17 | 2002-09-05 | Aaflowsystems Gmbh & Co Kg | filter body |
DE10227721B4 (en) * | 2002-06-21 | 2008-03-13 | Hermsdorfer Institut Für Technische Keramik E.V. | Process for producing a bundle of ceramic capillaries for a separation module |
JP4195824B2 (en) * | 2003-03-10 | 2008-12-17 | メタウォーター株式会社 | Filtration method |
US7578939B2 (en) * | 2004-12-09 | 2009-08-25 | Board Of Trustees Of Michigan State University | Ceramic membrane water filtration |
-
2012
- 2012-10-30 WO PCT/US2012/062519 patent/WO2013066841A1/en active Application Filing
- 2012-10-30 US US14/354,217 patent/US20140263034A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7226657B1 (en) * | 1998-11-04 | 2007-06-05 | Baxter International Inc. | Element provided with a fibrin layer, preparation and use thereof |
US20100056369A1 (en) * | 2008-08-29 | 2010-03-04 | Yunfeng Gu | Methods of Making Inorganic Membranes |
US20110025306A1 (en) * | 2009-08-03 | 2011-02-03 | Microfier, Inc. | Method and Apparatus for the Purification and Analytical Evaluation of Highly Purified Liquids |
JP2011205987A (en) * | 2010-03-30 | 2011-10-20 | Toray Ind Inc | Method for producing xylose syrup |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105268247A (en) * | 2014-07-23 | 2016-01-27 | 上海一鸣过滤技术有限公司 | Nanoscale porous metal filter medium and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
US20140263034A1 (en) | 2014-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gautam et al. | Performance evaluation and fouling analysis for reverse osmosis and nanofiltration membranes during processing of lignocellulosic biomass hydrolysate | |
EP3259304B1 (en) | Separation of lignin and sugars from organosolv liquors | |
Teella et al. | Separation of acetic acid from the aqueous fraction of fast pyrolysis bio-oils using nanofiltration and reverse osmosis membranes | |
Wei et al. | A review of membrane technology for bioethanol production | |
Qi et al. | Application of ultrafiltration and nanofiltration for recycling cellulase and concentrating glucose from enzymatic hydrolyzate of steam exploded wheat straw | |
Gaykawad et al. | Pervaporation of ethanol from lignocellulosic fermentation broth | |
Loulergue et al. | Air-gap membrane distillation for the separation of bioethanol from algal-based fermentation broth | |
CA2717298A1 (en) | Method of producing compound originating from polysaccharide-based biomass | |
DK2843061T3 (en) | Process for preparing a sugar solution | |
US20130292331A1 (en) | Ionic liquid recovery and purification in biomass treatment processes | |
Liu et al. | Membrane filtration: concentration and purification of hydrolyzates from biomass | |
Knozowska et al. | Membrane assisted processing of acetone, butanol, and ethanol (ABE) aqueous streams | |
JP2013162777A (en) | Method for producing sugar solution, sugar solution, and method for producing ethanol | |
Priya et al. | Comparative assessment of separation techniques for downstream processing of 2, 3-Butanediol | |
Nguyenhuynh et al. | A review on using membrane reactors in enzymatic hydrolysis of cellulose | |
US20140263034A1 (en) | Inorganic nanoporous membranes for high temperature pretreatment of lignocellulosic biomass | |
US9932648B2 (en) | Flow-through pretreatment of lignocellulosic biomass with inorganic nanoporous membranes | |
JP2013255457A (en) | Method for producing concentrated sugar solution and ethanol | |
Galiano et al. | Pervaporation and membrane distillation technology in biorefinery | |
JP2016007160A (en) | Manufacturing method of sugar solution, and manufacturing method of polysaccharide-based biomass-derived compound | |
Hai et al. | Membrane reactors for bioethanol production and processing | |
Amit et al. | Surface Modified Reverse Osmosis and Nano-Filtration Membranes for the Production of Biorenewable Fuels and Chemicals. | |
CN201643761U (en) | Multi-stage fractionation equipment | |
Roli et al. | Separation of xylose from glucose using pilot scale spiral wound commercial membrane | |
Malmali et al. | Continuous Hydrolysis of Lignocellulosic Biomass via Integrated Membrane Processes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12845336 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14354217 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12845336 Country of ref document: EP Kind code of ref document: A1 |